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Publication numberUS4591443 A
Publication typeGrant
Application numberUS 06/669,409
Publication dateMay 27, 1986
Filing dateNov 8, 1984
Priority dateNov 8, 1984
Fee statusPaid
Also published asCA1269183A1, DE3582304D1, EP0181211A2, EP0181211A3, EP0181211B1
Publication number06669409, 669409, US 4591443 A, US 4591443A, US-A-4591443, US4591443 A, US4591443A
InventorsRichard A. Brown, Robert D. Norris
Original AssigneeFmc Corporation
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Oxidizing contaminats with hydrogen peroxide and a hydratable polymeric compound
US 4591443 A
Abstract
The present invention is a process to oxidize a contaminant in a permeable subterranean formation by introducing an aqueous treating solution into the formation which solution contains hydrogen peroxide and a compound to control the mobility of the aqueous solution by increasing the viscosity, the density, or modifying the interfacial properties of the aqueous solution within the formation. The aqueous treating solution may also contain stabilizers for the hydrogen peroxide, free radical initiators, or free radical traps. Optionally, the formation may be pretreated to modify the permeability of the formation, to deactivate or remove hydrogen peroxide decomposition catalyst or to uniformly distribute free radical initiators therein.
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Claims(18)
What is claimed is:
1. A process for chemically oxidizing a contaminant in a permeable subterranean formation containing groundwater comprising introducing an aqueous treating solution into the formation said aqueous treating solution comprising 0.1% to 20% hydrogen peroxide and from 1 to 100 kilograms of a hydratable polymeric material per cubic meter of aqueous treating solution to provide sufficient viscosity to modify the distribution of the aqueous treating solution within the subterranean formation to provide sufficient hydrogen peroxide proximate to the contaminant to oxidize the contaminant to a less objectionable form yet minimize the distribution of hydrogen peroxide to portions of the subterranean formation free from the contaminant.
2. The process of claim 1 further including incorporating 0.5 to 40 kilograms per cubic meter of a surfactant into the aqueous treating solution thereby modifying the interfacial properties of the aqueous treating solution.
3. The process of claim 1 further including incorporating 0.5 to 40 kilograms per cubic meter of a phosphate salt into the aqueous treating solution thereby modifying the interfacial properties of the aqueous treating solution.
4. The process of claim 1 further including incorporating 0.5 to 40 kilograms per cubic meter of a densifier into the aqueous treating solution.
5. The process of claim 1 further including incorporating 0.5 to 40 kilograms per cubic meter of a phosphate salt as a densifier into the aqueous treating solution.
6. The process of claim 1 wherein an aqueous pretreatment fluid is introduced into the subterranean formation prior to the introduction of the aqueous treating solution, said pretreatment fluid comprising a compound selected from the group consisting of a hydrogen peroxide decomposition catalyst, a chelating agent, a free radical activator, and a phosphate salt.
7. The process of claim 6 wherein the aqueous pretreatment fluid comprises a phosphate salt.
8. The process of claim 6 wherein the aqueous pretreatment fluid comprises a free radical activator.
9. The process of claim 6 wherein the aqueous pretreatment fluid comprises a chelating agent.
10. The process of claim 6 wherein the aqueous pretreatment fluid comprises a potassium salt of phosphoric acid.
11. The process of claim 6 wherein the aqueous pretreatment fluid also comprises hydrogen peroxide.
12. The process of claim 6 wherein the aqueous pretreatment fluid comprises a hydrogen peroxide decomposition catalyst.
13. The process of claim 6 wherein the aqueous pretreatment fluid also comprises a free radical inhibitor.
14. The process of claim 13 wherein the free radical inhibitor is a compound selected from the group consisting of allyl alcohol, catechol, 1,10-orthophenanthroline, butene-1, 4-diol, phenol, resorcinol, and hydroquinone.
15. The process of claim 6 wherein the aqueous pretreatment fluid comprises a free radical activator and a free radical inhibitor.
16. The process of claim 15 wherein the free radical activator is a compound selected from the group consisting of an iron salt, a copper salt or a complex salt of iron or copper.
17. The process of claim 15 wherein the free radical inhibitor is a compound selected from the group consisting of allyl alcohol, catechol, 1,10-orthophenanthroline, butene-1, 4-diol, phenol, resorcinol, and hydroquinone.
18. The process of claim 1 wherein the hydratable polymeric material is a compound selected from the group consisting of hydratable polysaccharides, polyacrylamides, and polyacrylamide copolymers.
Description

This invention relates to a process for decontaminating a permeable subterranean formation by oxidizing the contaminent therein.

The contamination of soil, groundwater, or a subterranean formation is a serious environmental problem. It is estimated that there are in excess of 100,000 leaking underground gasoline storage tanks, and over 50,000 unlined industrial impoundments located above or near usable aquifers. Contaminants may include organic material, such as petroleum products, phenolics, halocarbons, alcohos, alcohols, and inorganic compounds. Prior conventional treatment technology consisted either of removing the contaminated formation material to a secure land fill or pumping of the the groundwater to the surface for treatment. Both of these techniques are limitec in effectiveness and can be very costly. They require long-term operations and are not certain to prevent the contamination from spreading further.

It is well known that many contaminants in a permeable subterranean formation can be rendered innocuous by oxidation. However, the mass transfer of oxygen into a subterranean formation is normally limited by the diffusion of oxygen gas or the solubility of oxygen in water. Therefore, it is normally difficult to introduce sufficient oxygen into a subterranean formation to oxidize a contaminant therein.

U.S. Pat. No. 3,846,290 to Raymond which is incorporated herein by reference teaches a process to eliminate hydrocarbon contaminants from subterranean groundwater by providing nutrients and oxygen thereby promoting biodegradation of a hydrocarbon contaminant by the microorganisms normally present in a subterranean formation. The process of Raymond is not effective for oxidizing compounds in a subterranean formation above the water table, inorganic compounds, or organic compounds present in concentrations which are toxic to the microoganism.

U.S. Pat. No. 4,401,569 to Jhaveri, which is incorporated herein by reference, teaches a process to treat ground and groundwater contaminated with hydrocarbon compounds. The process requires recirculating water through a contaminated subterranean formation thereby leaching the contaminants and reinjecting the oxidized leachant into the formation. The process of the Jhaveri patent is limited to biodegradable organic compounds located near the surface, and obviously cannot be used near structures which could be undermined by the recirculation of large quantitites of leachant. In addition the Jhaveri process requires the installation of tanks or other containers at the surface in which the biooxidation can take place.

In theory, in-situ oxidation of contaminants, by either a biological or a chemical mechanism offers the potential advantage of rendering contaminants harmless in a relatively short period of time at low cost. The problem with in-situ chemical oxidation is in controlling the positioning and the reaction of the treatment chemicals so that they preferentially react with the contaminant to give effective removal of the hazards associated with the contaminants.

An object of the present invention is an improved process to oxidize a contaminant within a permeable subterranean formation.

Another object of the present invention is an improved process to maintain an oxidizing environment within the subterranean formation thereby preventing undesirable anaerobic biological process from generating undesirable toxic products such as vinyl chloride or hydrogen sulfide.

A further object of this invention is an improved process to introduce an effective quantity of an environmentally acceptable oxidizing agent proximate to a contaminant within a subterranean formation whereby the contaminant can be oxidized to a more acceptable form while minimizing the total quantity of the oxidizing agent used.

The present invention provides a process wherein an aqueous treating solution is introduced into a subterranean formation, said aqueous treating solution containing an effective quantity of hydrogen peroxide and a mobility control agent selected from the group consisting of hydratable polymeric materials, interface modifiers, and densifiers thereby modifying the flow of the aqueous treating solution within the subterranean formation. The components of the aqueous treating solution may be introduced into the formation separately, sequentially, or as a complete formulation.

Hydrogen peroxide is a critical component of the aqueous treating solution, not only because it is completely miscible with water but also because it provides at least three possible oxidation mechanisms to oxidize a contaminant, ionic and free radical reactions of hydrogen peroxide and peroxides as well as reactions of elemental oxygen.

For the purpose of this invention it is essential for the hydrogen peroxide concentration to be at least about 0.1% by weight to attain reasonable reaction rates. Although any greater concentration may be used it is desirable to avoid concentrations greater than 20% for safety and economy. The preferable range is from 0.5% to 10%.

The hydrogen peroxide may be incorporated into the aqueous treating solution by any convenient means, either as a solution containing hydrogen peroxide or as a solid "peroxygen" compound which produces a solution of hydrogen peroxide upon contact with an aqueous solution. Suitable peroxygen compounds include sodium perborate, sodium carbonate peroxide, sodium pyrophosphate peroxide, or sodium peroxide. Alternatively, hydrogen peroxide may be generated within the aqueous treating solution by inserting an anode and cathode into the aqueous solution and passing a direct current between the anode and cathode thereby reducing oxygen to hydrogen peroxide at the cathode.

It is critical for the hydrogen peroxide to be distributed within the formation whereby sufficient hydrogen peroxide is located proximate to the contaminant to oxidize the contaminant to a less objectionable form yet minimize the distribution of hydrogen peroxide to portions of the subterranean formation free from the contaminant. It has been found that it is possible to use a mobility control agent such as a hydratable polymeric material, an interface modifier, a densifier, or combinations thereof to modify the flow of the aqueous treating material within the subterranean formation.

Hydratable polymeric materials are known to be useful to control the viscosity of hydraulic fluids in petroleum wells to facilitate the suspension of propping agents or packing agents. It has unexpectedly been found that by varying the viscosity of an aqueous treating fluid that the ratio of the horizontal flow to the vertical flow of the solution can be controlled in a permeable subterranean formation such as sand, gravel, or soil. In a formation containing groundwater it has been found that increasing the viscosity of the aqueous treating solution decreases the rate of diffusion of hydrogen peroxide into the groundwater from the aqueous treating solution and also decreases the rate of flow of the treating solution within the formation. Further, an aqueous treating solution with a very high viscosity can block the flow of groundwater through a contaminated portion of the subterranean formation during decontamination.

One skilled in the art will recognize that it is desirable to reduce the viscosity of the aqueous treating solution containing a hydratable polymeric material to facilitate easy removal thereof from the subterranean formation after the oxidation of the contaminant is completed. It is well known that the viscosity of the hydraulic fluids can be reduced or "broken" within a few hours by oxidizing agents such as catalyzed hydrogen peroxide.

Hydratable polymeric materials are also suitable for use in the present invention when the oxidation will be completed within a relatively short term. Typical polymeric materials useful for this invention include hydratable polysaccharides, polyacrylamides, and polyacrylamide copolymers. Particularly desirable polysaccharides include galactomanan gums, derivatives thereof, and cellulose derivatives. Typical polysaccharides include: guar gums, locust bean gum, karagya gum, sodium carboxymethyl guar, hydroxyethyl guar, hydroxypropyl guar, sodium hydroxymethyl cellulose, sodium carboxymethyl-hydroxyethyl cellulose, and hydroxyethyl cellulose. However, if it is desired that a polymeric material be used which is resistant to breaking in the presence of peroxygen compounds then a cross-linked interpolymer of an alpha-beta lower carboxylic acid as disclosed in U.S. Pat. No. 4,130,501 or the acrylic acid copolymers with polyallyl sucrose as disclosed in U.S. Pat. No. 3,499,844 would be selected. Both of the above patents are incorporated herein by reference.

Optionally, cross-linking agents may be added which increase the maximum temperature at which the hydratable polymers will retain the desired viscosity. These cross-linking agents are well known in the art and include polyvalent metal ions, such as chromium (III), aluminum (III), titanium (IV), and polyvalent anions, such as borates.

The quantity of the hydratable polymeric material used will depend on the viscosity desired for the aqueous treating solution. If a very viscous aqueous treating solution is desired from 10 to 100 kilograms of hydratable polymeric material per cubic meter of aqueous solution would be used. However, if only a moderate viscosity is desired then from 1 to 10 kilograms of hydratable polymeric material may be used.

For the purpose of this invention an "interface modifier" is defined as a compound that is capable either of increasing the capillary rise of the aqueous solution into a porous material or of increasing the ability of the aqueous solution to wet another surface. Surfactants which are known to reduce the surface tension of an aqueous solution are interface modifiers.

Surfactants can have the added benefit of preventing clays from swelling and dispersing material through the contaminated area and decreasing the activity of metals with respect to peroxide decomposition. Desirably from 0.5 kg to 40 kg of a surfactant is used per cubic meter of aqueous treating solution.

Soluble salts of orthophosphoric acid and soluble salts of condensed phosphonic acid have unexpectedly been found to increase the capillary rise of an aqueous solution into a porous material, therefore, and are also compounds which modify interfacial properites according to the present invention. For the purpose of this invention the soluble salts of orthophosphoric acid and the soluble salts of a condensed phosphoric acid will be referred to simply as "phosphate salts." Phosphate salts do not affect the surface tension of aqueous solutions. However, phosphate salts and surfactants both function as mobility control agents by increasing the capillary fringe above a water table thereby distributing the hydrogen peroxide contained in the aqueous treating solution proximate to a contaminant in the permeable subterranean formation above the water table. Desirably the usage rate of a phosphate salt is 0.5 kg to 40 kg per cubic meter.

A salt which, when dissolved in an aqueous solution, increases the density thereof is frequently referred to as a "densifier." Densifiers are used in well completion fluids to balance the hydrostatic pressure of a formation against the column of completion fluid in a well bore. By using a densifier to increase the density of an aqueous treating fluid it has been found that the mixing of the aqueous treating fluid with the groundwater is minimized. Therefore when a contaminant is located in a subterranean formation such as at the bottom of an aquifer or in the bottom layer of a subterranean body of water the addition of a densifier to the aqueous treating solution will distribute the aqueous treating solution containing hydrogen peroxide to the contaminant thereby minimizing the proportion of aqueous treating fluid distributed to portions of the subterranean formation free from the contaminant. Densifiers commonly used for hydraulically treating wells include sodium chloride, zinc chloride, calcium chloride, and sodium bromide. These salts may be useful as densifiers in the process of the present invention. However, it is more desirable to use a soluble salt of orthophosphoric acid or of a condensed phosphoric acid as a densifier.

Combinations of two or more mobility control agents may be desirable to distribute hydrogen peroxide contained in an aqueous treating solution proximate to a contaminant in a subterranean formation, for example, a hydratable polymeric material and a densifier, an interface modifier and a hydratable polymeric material, or a surfactant and a hydratable polymerial material.

Optionally a free radical activator (also called an "initiator") or a free radical trap (also called a "scavenger" or "inhibitor") may be incorporated into the aqueous treating solution if it is desired that an ionic or a free radical mechanism predominate. A combination of a free radical activator and a free radical trap may be particularly desirable when it is desired to delay the generation of free radicals until after the aqueous treating solution is introduced into the aqueous formation so that hydroxyl free radicals, when generated, are proximate to the contaminant. Alternatively, such a combination may be employed when it is desired that an ionic mechanism predominate initially to oxidize a contaminant and a free radical mechanism predominate subsequently either to depolymerize a hydratable polymeric material or to oxidize a second contaminant.

Free radical activators may be any transitional metal, preferably copper or iron, which can be present in the aqueous treating solution either as a simple ion or as a coordination compound. The desired usage rate of free radical activators will depend on many factors and can be determined by one skilled in the art without undue experimentation.

Free radical traps for peroxygen systems are also well known to those skilled in the art and include hydroxyphenols, amines, and polymerizable monomers which do not tend to form long chains. The latter include unsaturated alcohols and allylic compounds such as allyl alcohol. When both a free radical activator and a free radical trap are desired in an aqueous treating solution compounds capable of both complexing the metal ion and acting as an inhibitor are preferred. Such compounds include: catechol, and 9,10-orthophenanthroline. Preferable free radical traps or inhibitors are allyl alcohol, catechol, 9-10-orthophenanthroline, butene-1,4-diol, phenol, resorcinol, and hydroquinone.

The usage of the free radical scavengers will vary according to the efficacy of the compounds and the desired conditions of use. Generally, from 0.01 to 5 parts of a free radical scavenger are added per hundred parts of the aqueous treating solution; preferably 0.05 to 0.5 parts of the scavenger is added per hundred parts of aqueous treating solution.

It is critical for the present invention to avoid decomposition of sufficient hydrogen peroxide within the subterranean formation to retard or block the distribution of the aqueous treating solution proximate to the contaminant. Optionally a stabilizer for the hydrogen peroxide may be added to the aqueous treating solution. Suitable stabilizers are well known to those familiar with the art and are taught by Schumb et al, Hydrogen Peroxide, Reinhold Publishing Corporation, New York (1955) which is incorporated herein by reference in its entirety.

For optimum results it may be critical for the subterranean formation to be pretreated either to minimize decomposition of hydrogen peroxide or to distribute a free radical activator or a hydrogen peroxide decomposition catalyst uniformly within the contaminanted area. This may be accomplished by introducing a pretreatment fluid into the formation. To minimize the decomposition of hydrogen peroxide, the pretreatment fluid may contain a compound which inactivates a hydrogen peroxide decomposition catalyst by reacting with the decomposition catalyst, by complexing the decomposition catalyst, by dissolving and/or removing the decomposition catalyst or by deactivating catalytically active surfaces of the permeable subterranean formation. An organic or inorganic complexing agent or chelating agent is particularly desirable for use in a penetrating fluid. Suitable pretreatment fluids can be easily selected by one skilled in the art by referring to Schumb et al and the prior art. Phosphate salts are particularly desirable for incorporation into pretreatment fluids. Orthophosphate salts are known to precipitate many catalysts for hydrogen peroxide or precipitate on catalytically active surfaces. Salts of condensed phosphates, particularly pyrophosphate salts are well known as stabilizers for peroxygen systems, and other condensed phosphates are well known to be suitable to complex, inactivate, or solubilize polyvalent ions which include decomposition catalysts for hydrogen peroxide. A free radical inhibitor may also be incorporated into the pretreatment fluid to minimize hydrogen peroxide decomposition.

Pretreatment of a permeable subterranean formation may also be desirable to either improve the permeability of a formation containing clays or block the flow of aqueous treating solution to a portion of the formation not containing a contaminant. Pretreatment with fluids containing potassium phosphate and surfactants is particularly desirable to improve the permeability of a formation containing a clay while pretreatment with sodium salts or other clay swelling agents is desirable to block the aqueous treating solution from contact with an uncontaminated portion of a formation.

It is particularly desirable to incorporate phosphate salts into an aqueous treating solution and/or a pretreating fluid because the phosphate salts are useful as pH buffers and provide the multiple function as a stabilizing agent, a mobility control agent, a complexing/precipitating agent, and a surface deactivator.

The following examples are presented to instruct one skilled in the art of the best mode of practicing the present invention and are not intended to limit the scope of the invention.

EXAMPLE 1

The effect of mobililty control agents for modifying the distribution of an aqueous treating solution within a porous subterranean formation was demonstrated by adding 1 g/l of a polyol surfactant (Pluronic™ F87) and 0.1 g/l carboxyvinyl polymer hydratable polymeric material (Carbopol™ 940) to a 1% solution of hydrogen peroxide. Ten ml of the solution was allowed to flow onto a bed of dry sand. The wetted sand had an average diameter and depth of 5.1 cm by 1.9 cm compared with 3.8 cm by 3.2 cm observed for a 1% hydrogen peroxide solution without the mobility control agents.

EXAMPLE 2

Aqueous treating solutions containing 1% hydrogen peroxide were prepared according to Table I to demonstrate the relative effect of common hydratable polymeric materials on an aqueous solution of hydrogen peroxide. Viscosities are reported in arbitrary units using a NL Baroid Rheometer at 600 rpm. The hydratable polymeric materials used were a hydroxypropyl guar (Celanese WSP-05-1001-01), a carboxymethyl cellulose (Hercules CMC-6-CT-L), and a polyacrylamide (Cort 320).

EXAMPLE 3

The effect of free radical activators and inhibitors on the rate of breaking of aqueous treating solutions was determined using the same concentration of hydratable polymeric material used in Example 2. Experimental conditions and observations are presented in Table II.

The stability of hydrogen peroxide was determined in the hydroxypropyl guar and carboxymethyl cellulose solutions. After 18-24 hours at least 90% of the initial hydrogen peroxide was still retained both in the absence and presence of the sodium nitrite.

EXAMPLE 4

The effect of controlling the mobility of an aqueous treating solution by increasing the specific gravity of the solution with a densifier was demonstrated by adding 50 ml of a 4.1% solution of hydrogen peroxide to 450 ml of water in a 600 ml tall-form beaker. The concentrations of hydrogen peroxide from the top and at the bottom of the beaker were found respectively to be 0.38% and 0.55%. When a similar solution saturated with potassium tripolyphosphate was added the concentrations of hydrogen peroxide were found to be 0.38% and 0.61% respectively.

EXAMPLE 5

The effect of a surfactant as a mobility control agent was demonstrated by measuring the change of capillary rise of an aqueous treating solution in a sand column. Four 457 mm long 15 mm ID glass columns were filled with 100 g Marietta sand on top of a glass wool plug. The tubes were immersed with 25.4 mm of sand below the surface of the test liquids and the height of capillary rise in tubes was measured with time as reported in Table III. Unexpectedly it was observed that both orthophosphates and condensed phosphates were very effective mobility control agents. The solutions tested were tap water, an orthophosphate solution containing 0.4 g/l KH2 PO4, 0.6 g/l Na2 HPO4, g/l NH4 Cl, 0.2 g/l MgSO4, and 0.02 g/l MnSO4.H2 O, a condensed phosphate solution containing 1 g/l NH4 C1, and 1 g/l Na5 P3 O8, and 1 g/l carboxyvinyl polymer surfactant (Pluronic™ F87).

EXAMPLE 6

Hydrogen peroxide was demonstrated to be effective as a pretreatment fluid by the following simulation. Approximately 50 grams of a soil containing clay was placed in a 100 ml beaker. The soil was slurried for 30 seconds with 100 ml of 0.1% hydrogen peroxide. Aliquots of the liquid phase were analyzed for hydrogen peroxide content after 3 and 15 minutes. The hydrogen peroxide was decanted and another 100 ml of the hydrogen peroxide solution added and analyzed as before. The process was repeated for a total of six cycles. The results appear as Table IV and show the hydrogen peroxide stability increased with successive cycles.

EXAMPLE 7

The effect of a multiple step pretreatment, as shown in Table V, was demonstrated using the following technique:

Pretreatment--A 40 g sample of a soil containing clay was soaked at 20° C. in 100 ml of a 0.5% solution of an additive and after 16 hours the pretreatment fluid was decanted.

(A1)--The soil from the preliminary treatment was slurried with 100 ml of 0.1% H2 O2 and after 2 hours standing the assay of the supernatant solution was recorded in Table V and the solution was decanted.

(A2)--The soil from step A1 was slurried with another 100 ml portion of 0.1% H2 O2 and the assay of the supernatent solution was determined after 1, 2, and 18 hours.

Treatment B1 and B2 --The treatments were the same as the A1 and A2, except that the solution used in step B2 contained 0.04% KH2 PO4, 0.06% Na2 HPO4, 0.1% NH4 Cl, and 0.1% H2 O2 to improve the stability of the hydrogen peroxide in the aqueous treating solution.

It is well known from chapter 7 of Schumb et al, that hydrogen peroxide is a versatile oxidizing agent. Table VI lists a few typical compounds which are oxidized by hydrogen peroxide and typical preferred conditions.

The following examples illustrate how a contaminated site would be treated according to the present invention.

EXAMPLE 8

A 100 m3 site is found to be contaminated with 0.2 kg phenol per cubic meter. The contaminant is located in a coarse sandy aquifer above a confining layer in which flow rates of 200 1/min are possible. The site is prepared by placing injection wells/or galleries up gradient of the contaminant, screened at the saturated zone, and a pumping well down gradient also screened at the saturated zone. The site is then preflushed with a solution containing 20 ppm ferrous sulfate adjusted to a pH of 4. The preflush is continued until the pH at the recovery well is below 6. At this point a 1% hydrogen peroxide solution containing at least 500 mg/l total phosphates, pH adjusted to 5-6, is added to the injection wells.

The pumping/injection rate is balanced at 50 liters/min. If preliminary soil tests of the site show that peroxide decomposition is 20-50% over the first hour the adjusted minimum peroxide requirement would be 12.8-20.4 thousand litre hydrogen peroxide addition is continued until the phenol level is decreased to acceptable levels.

EXAMPLE 9A

If the phenol contamination were located in a highly permeable sand above the water table an important consideration would be to maximize the horizontal spread of the peroxide solution. If the phenol contamination was 1.83 meters below ground level injection of a thickened 1% H2 O2 aqueous treating solution having a viscosity of 35 cps (having a horizontal to vertical flow of 2.7:1) through 0.3 M deep injection wells on a 4.2 meter spacing would provide sufficient horizontal flow to cover the contaminant. Any hydratable polymeric material would be accepted as a thickening agent.

EXAMPLE 9B

Alternatively if the phenol contamination were located just above the confining barrier and in the saturated zone, more efficient treatment could be obtained by using a densified treatment fluid. In this case the addition of high levels of ortho and pyrophosphates would be introduced to the treatment solution to pH 5. Placement of the injection and recovery wells in close proximity to the confining layer would also be desirable.

              TABLE I______________________________________Viscosity of Aqueous Treating SolutionsContaining 1% Hydrogen PeroxidePolymer    Relative Viscosityg/l Type       Initial 1 hr  3 hr 6 hr  18 hr                                        24 hr______________________________________6.1 Hydroxy-   54      53    --   --    22   8    propyl    guar5.0 Carboxy-    9       7    5.5  --    --   2    methyl    cellulose1.7 Polyacryl- 17.5    13    7.7  4.5   --   --    amide______________________________________

              TABLE II______________________________________Effect of Inhibitors and Acceleratorson Aqueous Treating Solution(1% H2 O2)Polymer Additive   Relative Viscosity                    Ini-g/l Type    g/l    Type  tial 1 hr 3 hr 6 hr 18 hr                                             24 hr______________________________________6.1 HPG     .83    NaNO2                    54   54   --   --   120  2605.0 CMC     .83    NaNO2                     8    9   13   --   --    141.7 PAA     10.0   1,4-BD                    18   19   30   54   --   --1.7 PAA     0.7    FeSO4                    18    4   --   --   --   --______________________________________ HPG = Hydroxypropyl Guar CMC = Carboxymethyl Cellulose PAA = Polyacrylamide 1,4-BD = 1,4but-2-enediol

              TABLE III______________________________________Capillary Rise of AqueousTreating Solutions     Capillary Rise (mm)Solution    30 min.     60 min. 180 min.______________________________________Tap Water    89          89      89Orthophosphate       133         140     152SolutionCondensed   146         159     171PhosphateSolutionSurfactant  121         127     127______________________________________

              TABLE IV______________________________________Effect of H2 O2 Preflush onH2 O2 Stability    % of Original H2 O2 Remaining AfterCycle      3 minutes    15 minutes______________________________________1          11           22          19           33          28           64          23           75          39           166          --           41______________________________________

                                  TABLE V__________________________________________________________________________Effect of Pretreatment of Soils on H2 O2 Stability            Treatment A     Treatment B            % H2 O2 Remaining                            % H2 O2 Remaining            A1 A2        Final                            B1 B2        FinalRun   Pretreatment Agent            2 Hr               1 hr                  2 Hr                     18 Hr                         pH 2 Hr                               1 Hr                                  2 Hr                                     18 Hr                                         pH__________________________________________________________________________1  None          50 60 50 20  6.9                            70 80 70 30  6.72  ethylenediaminetetraacetate            100               100                  80 70  5.1                            100                               90 90 --  5.23  sodium tripolyphosphate            40 90 60 30  8.2                            70 100                                  90 70  7.04  nitrilotriacetate sodium salt            30 50 30 10  8.4                            70 80 -- 30  7.15  soda ash      20 20 10  0  10.3                            50 70 60 20  8.36  long chain polyphosphate            50 90 70 10  7.6                            90 100                                  100                                     50  6.97  triethanol amine            30 20 10 10  10 55 80 60 20  8.0__________________________________________________________________________

              TABLE VI______________________________________Treatment Conditions for Various Compounds                                 Minutes     Weight Ratio                Minimum     of H2 O2          ContactCompounds to Compound pH       Catalyst                                 Time______________________________________H2 S 1:1         <6.5     Fe+2                                 5 min.HS-  1.03:1      6.5-7.5  Fe+2                                 1 min.S-2  4.25:1      >8       Fe+2                                 2 min.RSH, RSSR >5:1 molar  >8       Fe+2                                 5 min.RSR       >2:1 molar  2-6      Fe+2                                 1-2 hrs.hydroquinone     4:1         <6.5     --     5 min.CN-  1.3:1       8.5-10   Cu+                                 .5-1 hr.formaldehyde     2.3:1       >8       --     5 min.phenol    5.06:1      5-6      Fe+2                                 10 min.______________________________________
Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3499844 *Aug 21, 1967Mar 10, 1970Fmc CorpMethod of preparing an aqueous hydrogen peroxide gel
US3529666 *Jul 30, 1968Sep 22, 1970Dow Chemical CoMethod of improving permeability of geologic formations by removal of organic material therefrom
US3754599 *Dec 15, 1971Aug 28, 1973Marathon Oil CoUse of micellar solutions to improve perforating process
US3846290 *Sep 29, 1972Nov 5, 1974Sun Research DevelopmentReclamation of hydrocarbon contaminated ground waters
US3896879 *Oct 24, 1974Jul 29, 1975Kennecott Copper CorpStimulation of recovery from underground deposits
US4130501 *Sep 20, 1976Dec 19, 1978Fmc CorporationStable viscous hydrogen peroxide solutions containing a surfactant and a method of preparing the same
US4234433 *Oct 4, 1978Nov 18, 1980Marathon Oil CompanyRecovery of petroleum with chemically treated high molecular weight polymers
US4370241 *Nov 27, 1979Jan 25, 1983Degussa AgWith hydrogen peroxide with iron or copper catalysts with activator
US4388194 *Sep 4, 1981Jun 14, 1983Fmc CorporationHydrogen sulfide abatement in geothermal steam systems
US4401569 *Jul 9, 1981Aug 30, 1983Groundwater Decontamination Systems, Inc.With microorganisms
US4440651 *Nov 9, 1981Apr 3, 1984Standard Oil CompanyUse of peroxide in waterflood oil recovery
US4453597 *Feb 16, 1982Jun 12, 1984Fmc CorporationStimulation of hydrocarbon flow from a geological formation
US4464268 *Jan 11, 1982Aug 7, 1984Texaco Inc.Injection aqueous colution of hydrogen peroxide, an acid and a surfactant
US4495996 *Dec 1, 1983Jan 29, 1985Atlantic Richfield CompanyMethod for scale removal and scale inhibition in a well penetrating a subterranean formation
US4524829 *Sep 19, 1984Jun 25, 1985Halliburton CompanyMethod of altering the permeability of a subterranean formation
DE2533775A1 *Jul 29, 1975Feb 3, 1977Guenter Dipl Chem Dr GassmannVerfahren zur beseitigung offener und latenter veroelungen
GB2084560A * Title not available
Non-Patent Citations
Reference
1Canter et al., "Ground Water Pollution Control" Lewis Publishers, 1985, pp. 131-149.
2 *Canter et al., Ground Water Pollution Control Lewis Publishers, 1985, pp. 131 149.
3Schroeder, "Biological Relationships" Oligodynamic Press, 1971, pp. 21-51.
4 *Schroeder, Biological Relationships Oligodynamic Press, 1971, pp. 21 51.
5Schumb et al., "Hydrogen Peroxide" Reinhold Publishing Corp., 1955, pp. 411-416, and 613-618.
6 *Schumb et al., Hydrogen Peroxide Reinhold Publishing Corp., 1955, pp. 411 416, and 613 618.
7 *The New Encyclopaedia Britannica, vol. 9, Macro, 15th Edition, Benton (1974) Chicago, pp. 109 114.
8The New Encyclopaedia Britannica, vol. 9, Macro, 15th Edition, Benton (1974) Chicago, pp. 109-114.
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4749491 *Jul 23, 1987Jun 7, 1988E. I. Du Pont De Nemours And CompanyMicrobiological decomposition of chlorinated aliphatic hydrocarbons
US4848460 *Nov 4, 1988Jul 18, 1989Western Research InstituteContained recovery of oily waste
US4992379 *Feb 5, 1987Feb 12, 1991Hanby John DField test for aromatics in groundwater
US5006250 *Dec 4, 1987Apr 9, 1991The Board Of Trustees Of The Leland Stanford Junior UniversityIn-situ biodegradation of halogenated aliphatic compounds as impurities in underground water supply by microbacteria
US5008019 *May 15, 1989Apr 16, 1991Waste-Tech Services, Inc.Displacing with aqueous alkaline polymer solution
US5038864 *May 10, 1990Aug 13, 1991Marathon Oil CompanyProcess for restoring the permeability of a subterranean formation
US5154836 *Jun 14, 1990Oct 13, 1992Ensci, Inc.Process for treating contaminants in aqueous-based materials
US5262018 *Aug 12, 1991Nov 16, 1993Fmc CorporationMetals removal from aqueous peroxy acids or peroxy salts
US5266213 *Nov 28, 1990Nov 30, 1993Gillham Robert WCleaning halogenated contaminants from groundwater
US5286141 *Feb 12, 1993Feb 15, 1994Vigneri Ronald JPlurality of mutually spaced wells, injection of hydrogen peroxide; monitoring of pH changes
US5302287 *Sep 11, 1992Apr 12, 1994Tuboscope Vetco InternationalBreaking up soil, mixing with water, biodegradable detergent, separating floating contaminants, repeating, adding activator for microorganisms which remove remaining contaminants, separating, washing, returning, recycling decontaminated water
US5316664 *Oct 23, 1992May 31, 1994Canadian Occidental Petroleum, Ltd.Separation of sand from hydrocarbons using chemicals such as nonionic surfactants of ethoxylated alkylphenols and dialkylphenols
US5340467 *Oct 24, 1991Aug 23, 1994Canadian Occidental Petroleum Ltd.From tar sand; slurrying with ethylene oxide alkylphenol adduct, aeration
US5405531 *Feb 16, 1993Apr 11, 1995Geo-Microbial Technologies, Inc.Method for reducing the amount of and preventing the formation of hydrogen sulfide in an aqueous system
US5520483 *Feb 10, 1994May 28, 1996Vigneri; Ronald J.Method and system for remediation of groundwater contamination
US5614474 *Oct 18, 1994Mar 25, 1997Exxon Research And Engineering CompanyPolymer-surfactant fluids for decontamination of earth formations
US5667690 *Mar 22, 1996Sep 16, 1997Nederlandse Organisatie Voor Toegepast - NatuurwetenschappelijkProcess for removing noxious compounds
US5741427 *Mar 14, 1996Apr 21, 1998Anesys Corp.Soil and/or groundwater remediation process
US5741761 *Nov 19, 1996Apr 21, 1998Exxon Research And Engineering CompanyPolymer-surfactant fluids for decontamination of earth formations (LAW181)
US5750392 *Sep 15, 1994May 12, 1998Geo-Microbial Technologies, Inc.Consisting of nitrite or nitrate ions to enhance growth of denitrifying bacteria
US5773194 *Aug 29, 1996Jun 30, 1998Konica CorporationPhotosensitivity; durability
US5797701 *Feb 27, 1997Aug 25, 1998Continuium Environmental Inc.Oxidation of petrochemical pollutant such as anthrcene and naphthacene contaminating soil, with hydrogen peroxide to nonpollutant anthraquinone and naphthaquinone; soil treatment
US5821113 *Feb 29, 1996Oct 13, 1998Envorflow Inc.Method of reducing contamination and composition for use in the method
US5893975 *Apr 23, 1997Apr 13, 1999Roux Associates, Inc.Enhanced subsurface flow constructed wetland
US5967230 *Nov 14, 1997Oct 19, 1999Cooper; KentHydrocarbon contaminants, oxidizing agent introduced to release a free radical in a fenton-type reaction
US6001769 *Sep 25, 1997Dec 14, 1999Correctivaction, LlcCompositions and methods for the remediation of chemical contamination in subsurface water bearing geological formations
US6131661 *Aug 3, 1998Oct 17, 2000Tetra Technologies Inc.Drilling the borehole with fluid to form an oxidation degradable filtercake; adding soluble organic hydroperoxide fluid thermoactivatable at the downhole temperature; allowing oxidizing agent to form, degrade filtercake; flushing
US6143698 *Dec 4, 1998Nov 7, 2000Tetra Technologies, Inc.Drilling borehole while circulating mud which comprises a polysaccharide and finely divided solids dispersed to form a filtercake on surfaces of borehole essentially free of oxidants and bromine; introducing filtercake removal fluid
US6158924 *Apr 20, 1999Dec 12, 2000Athens; NickSoil and groundwater decontamination system with vacuum extraction
US6206098Sep 7, 1999Mar 27, 2001Kent CooperIn situ water and soil remediation method and system
US6352387Dec 2, 1999Mar 5, 2002Robert A. BriggsRecirculation-enhanced subsurface reagent delivery system
US6502633Mar 26, 2001Jan 7, 2003Kent CooperIn situ water and soil remediation method and system
US6576145Jun 18, 2001Jun 10, 2003Continuum Environmental, LlcSeparating hydrocarbons from a mixture of the hydrocarbons and a particulate mineral substrate, comprising mixing of mixture with water to form a slurry, addition of oxidizer to release hydrocarbons form the substrate, then separation
US6623211 *May 23, 2001Sep 23, 2003Rutgers UniversityRemediation of contaminates including low bioavailability hydrocarbons
US6746180 *Jun 12, 2003Jun 8, 2004Rutgers, The State University Of New JerseyOxidation in presence of transition metal salt, chelate compound and ph buffer; preventing precepitation or solubilization heavy metal byproduct contamination
US6843618Dec 14, 2001Jan 18, 2005William L. LundyTreating soils and ground water with aqueous solution containing peroxide and a water-soluble chelating agent; reacting chelate compound with the peroxide to catalytically form oxidizing agent; oxidizing contaminant
US6884884Jun 10, 2002Apr 26, 2005Rhodia, Inc.Galactomannan compositions and methods for making and using same
US6923596Oct 2, 2003Aug 2, 2005Lessard Environmental, Inc.Injection of hydrogen peroxide and bacteria into wells, for purification of soils and subterranean water; water treatment
US7045493 *Dec 28, 2004May 16, 2006Arkema Inc.Stabilized thickened hydrogen peroxide containing compositions
US7056061 *Mar 24, 2004Jun 6, 2006Rutgers, The State University Of New JerseyRemediation of contaminates including low bioavailability hydrocarbons
US7156178Sep 23, 2003Jan 2, 2007Bj Services CompanyUsing buffered hydrogen peroxide or per-acids to remove polymers while simultaneously dissolving encountered calcium carbonate deposits
US7160471 *Oct 27, 2004Jan 9, 2007Westinghouse Savannah River Company, LlcIn-situ generation of oxygen-releasing metal peroxides
US7364386Dec 13, 2006Apr 29, 2008Surbec Environmental LlcIn-situ surfactant and chemical oxidant flushing for complete remediation of contaminants and methods of using same
US7381337Jul 16, 2004Jun 3, 2008Lessard Environmental, Inc.Oxidizing agent, inorganic thickener and salts and diluent; soil, groundwater, sediment and/or bedrock treatment; placement control, reduced postcleanup; safer, lower cost
US7585826 *Mar 22, 2007Sep 8, 2009Well-Being Biochemical Corp.applying catalytic ionic salt, buffers and a mixture of a reducing coenzyme and oxidizers or sulfide, to crops, fruits, humans, protective clothing or devices and medical equipment
US7708496Oct 31, 2007May 4, 2010Surbec-Art Environmental, L.L.C.In-situ surfactant and chemical oxidant flushing for complete remediation of contaminants and methods of using same
US8480903 *Nov 16, 2012Jul 9, 2013Jesse Clinton Taylor, IIISystems and methods for in-situ contaminant remediation
US8556537Feb 24, 2010Oct 15, 2013Geo-Cleanse International, Inc.Manganese-mediated redox processes for environmental contaminant remediation
US8575075Feb 22, 2010Nov 5, 2013Fmc CorporationOil-field viscosity breaker method utilizing a peracid
US8628659 *Feb 15, 2013Jan 14, 2014Jesse Clinton Taylor, IIIIn-situ contaminant remediation systems and methods
US8673152May 3, 2013Mar 18, 2014Alcoa Inc.Methods for polishing wastewater utilizing a bed of commingled bauxite residue and iron filings
WO1994018395A1 *Feb 9, 1994Aug 18, 1994Ronald J VigneriMethod and system for remediation of groundwater contamination
WO1994018396A1 *Feb 10, 1994Aug 18, 1994Ronald J VigneriMethod and system for remediation of groundwater contamination
WO2001017703A1 *Sep 7, 2000Mar 15, 2001James CareyIn situ water and soil remediation method and system
WO2005009909A1 *Jul 16, 2004Feb 3, 2005Lawrence H LessardGel-based remedial additive for remediation of environmental media and method of use
WO2010077570A2 *Dec 4, 2009Jul 8, 2010Fmc CorporationAcrylamide removal from aqueous fluid bodies
Classifications
U.S. Classification210/747.8, 210/759, 166/300, 210/763, 166/307, 166/312, 210/752
International ClassificationA62D101/45, A62D101/40, C02F1/72, C02F3/00, A62D101/28, B09C1/08, B09C1/02, A62D101/47, A62D101/20, A62D3/00, C09K17/00, C02F3/02, C12S99/00, A62D3/38
Cooperative ClassificationA62D2101/45, B09C1/08, A62D2101/20, C02F1/722, A62D3/38, A62D2101/47, A62D2101/28, A62D2101/40
European ClassificationC02F1/72C, B09C1/08, A62D3/38
Legal Events
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Aug 26, 1998ASAssignment
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Feb 14, 1998REMIMaintenance fee reminder mailed
Nov 1, 1993FPAYFee payment
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Oct 12, 1989FPAYFee payment
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Feb 24, 1987ASAssignment
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Aug 26, 1986CCCertificate of correction
Nov 8, 1984ASAssignment
Owner name: FMC CORPORATION 2000 MARKET ST. PHILADELPHIA, PA 1
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Effective date: 19841101